CA1308520C - Textile aftertreatment agents - Google Patents
Textile aftertreatment agentsInfo
- Publication number
- CA1308520C CA1308520C CA000559875A CA559875A CA1308520C CA 1308520 C CA1308520 C CA 1308520C CA 000559875 A CA000559875 A CA 000559875A CA 559875 A CA559875 A CA 559875A CA 1308520 C CA1308520 C CA 1308520C
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- CA
- Canada
- Prior art keywords
- mixture
- formula
- moles
- ammonia
- homopolymer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
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Classifications
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P5/00—Other features in dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form
- D06P5/02—After-treatment
- D06P5/04—After-treatment with organic compounds
- D06P5/08—After-treatment with organic compounds macromolecular
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L39/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen; Compositions of derivatives of such polymers
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
- D06P1/44—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders
- D06P1/52—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders using compositions containing synthetic macromolecular substances
- D06P1/5207—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
- D06P1/5214—Polymers of unsaturated compounds containing no COOH groups or functional derivatives thereof
- D06P1/5242—Polymers of unsaturated N-containing compounds
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
- D06P1/44—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders
- D06P1/64—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders using compositions containing low-molecular-weight organic compounds without sulfate or sulfonate groups
- D06P1/642—Compounds containing nitrogen
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S8/00—Bleaching and dyeing; fluid treatment and chemical modification of textiles and fibers
- Y10S8/916—Natural fiber dyeing
- Y10S8/917—Wool or silk
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S8/00—Bleaching and dyeing; fluid treatment and chemical modification of textiles and fibers
- Y10S8/916—Natural fiber dyeing
- Y10S8/918—Cellulose textile
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Polymers & Plastics (AREA)
- Medicinal Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Organic Chemistry (AREA)
- Coloring (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
- Nitrogen Condensed Heterocyclic Rings (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Treatment And Processing Of Natural Fur Or Leather (AREA)
Abstract
IMPROVEMENTS IN OR RELATING TO ORGANIC COMPOUNDS
Abstract of the Disclosure A mixture of a textile auxiliary (T) obtained by reacting epichlorohydrin and ammonia in defined mole ratio, and a polymeric compound (P) which is a water-soluble homopolymer of a mono- or di-allylamine, or a water-soluble copolymer consisting of mono-, di-or tri-allylamine units may be used as an aftertreatment agent for fixation of anionic and sulphur dyeings on cellulosic fibres. The treated dyeings have better fastness properties than dyeings treated with either (T) or (P) alone.
Abstract of the Disclosure A mixture of a textile auxiliary (T) obtained by reacting epichlorohydrin and ammonia in defined mole ratio, and a polymeric compound (P) which is a water-soluble homopolymer of a mono- or di-allylamine, or a water-soluble copolymer consisting of mono-, di-or tri-allylamine units may be used as an aftertreatment agent for fixation of anionic and sulphur dyeings on cellulosic fibres. The treated dyeings have better fastness properties than dyeings treated with either (T) or (P) alone.
Description
- l - Case lS0-5l5g IMPRLVEMENTS IN CR RELAIING TO GRGANIC COMPOUNDS
This invention relates to textile aftertreatment agents for improving the fastness properties of dyeings and printings.
The invention provides a synergistic mixture containing as active ingredients a textile auxiliary (T) and a polymeric comp~und (P), in which T is the product of a 2-step reaction comprising the steps of l) reacting an epihalohydrin with aqueous ammonia at 50-90C at an initial mole ratio of 4 moles epihalohydrin ~0 to 8-lO moles of ammonia, and 2) reacting the product of step l), after removal of excess ammonia, with a further O.l to 0.5 moles of epihalohydrin and P is a water-soluble homopolymer of a mono- or di-allylamine, or a water-soluble copolymer consisting of mono-, di- or tri-allylamine units.
In the production of T, the initial mole ratio in step l) is preferably 4 moles epihalohydrin to 9 moles ammonia. The product of step l) is preferably crosslinked in step 2) with 0.3 - 0.5 moles epihalohydrin, more preferably 0.4 moles. The epihalohydrin is preferably epichlorohydrin. The reaction product is preferably neutralized with a mineral acid, particularly sulphuric acid.
The water-soluble allylamine polymer P is preferably a) a homopolymer of a monoallylamine or b) a homopolymer of a diallylamine 5 or c) a copolymer of monomer units selected from monoallylamines, diallylamines and triallylamines.
This invention relates to textile aftertreatment agents for improving the fastness properties of dyeings and printings.
The invention provides a synergistic mixture containing as active ingredients a textile auxiliary (T) and a polymeric comp~und (P), in which T is the product of a 2-step reaction comprising the steps of l) reacting an epihalohydrin with aqueous ammonia at 50-90C at an initial mole ratio of 4 moles epihalohydrin ~0 to 8-lO moles of ammonia, and 2) reacting the product of step l), after removal of excess ammonia, with a further O.l to 0.5 moles of epihalohydrin and P is a water-soluble homopolymer of a mono- or di-allylamine, or a water-soluble copolymer consisting of mono-, di- or tri-allylamine units.
In the production of T, the initial mole ratio in step l) is preferably 4 moles epihalohydrin to 9 moles ammonia. The product of step l) is preferably crosslinked in step 2) with 0.3 - 0.5 moles epihalohydrin, more preferably 0.4 moles. The epihalohydrin is preferably epichlorohydrin. The reaction product is preferably neutralized with a mineral acid, particularly sulphuric acid.
The water-soluble allylamine polymer P is preferably a) a homopolymer of a monoallylamine or b) a homopolymer of a diallylamine 5 or c) a copolymer of monomer units selected from monoallylamines, diallylamines and triallylamines.
- 2 - Case 150-5159 In each case the allylamine may be in free base, acid addition salt or quaternary a~monium salt form.
More preferably, P is a water-soluble polymer of type a) - c) above, in which any monoallylamine ccmponent is of formula I
~ R l CH2 = C - CH2 - N
\R2 or an acid addition salt thereof, or of formula II
~ ~ Rl a CH2 = C - CH2 - N R2a A
\ R3 any diallylamine camponent is of formula R
CH2 = C - CH2 ~
N - Rl III
CH2 = C - CH2 or an acid addition salt thereof, or of formula R
CH2 = C - CH~ 6~ _ " R3 R ~ N A ~3 IV
CH2 = C - CH2 R4 and any triallylamine component is of formula - 3 - Case 150-5159 (~H2 = C - c~3-~r----N
or an acid addition salt thereof, or of formula (CH2 = C - CH2~ N Rla ~ VI
in which R is hydrogen or methyl, preferably hydrogen Rl and R2 are independently hydrogen, Cl_4alkyl, benzyl, 2-hydroxyethyl, 2-hydroxypropyl, 3-hydroxypropyl or cyclohexyl, preferably hydrogen Rla~ R2a~ R3 and R4, independently, have any significance of Rl and R2 other than hydrogen, or Rl and R2, Rla and R2a or R3 and R4 may together with the nitrogen atom to which they are attached form a piperidine, morpholine or pyrrolidine ring, and A~3 is an anion, preferably chloride, sulphate or phosphate.
Most preferably, P is a hcnopolymer of allylamine tthe ccmpound of formula I in which R, Rl and R2 are all hydrogen) or of diallylamine (the ccmpound of formula III in which both R's and R
are all hydrogen), or a copolymer of these two compounds.
The proportion of P to T in the mixture according to the invention is such that a synergistic effect exists, that is, that the measured effect of the mixture is superior to the additive effect of the separate ccmponents. Preferably the mixture contains from 30:70 to 70:30 parts by weight of the components (measured as dry active material, as salt in the case of T, as free base in the case of P), more preferably frcm 40:60 to 60:40, particularly 50:50. The mixture is prepared by simple mixing of the components, preferably in the form of their aqueous solutions.
More preferably, P is a water-soluble polymer of type a) - c) above, in which any monoallylamine ccmponent is of formula I
~ R l CH2 = C - CH2 - N
\R2 or an acid addition salt thereof, or of formula II
~ ~ Rl a CH2 = C - CH2 - N R2a A
\ R3 any diallylamine camponent is of formula R
CH2 = C - CH2 ~
N - Rl III
CH2 = C - CH2 or an acid addition salt thereof, or of formula R
CH2 = C - CH~ 6~ _ " R3 R ~ N A ~3 IV
CH2 = C - CH2 R4 and any triallylamine component is of formula - 3 - Case 150-5159 (~H2 = C - c~3-~r----N
or an acid addition salt thereof, or of formula (CH2 = C - CH2~ N Rla ~ VI
in which R is hydrogen or methyl, preferably hydrogen Rl and R2 are independently hydrogen, Cl_4alkyl, benzyl, 2-hydroxyethyl, 2-hydroxypropyl, 3-hydroxypropyl or cyclohexyl, preferably hydrogen Rla~ R2a~ R3 and R4, independently, have any significance of Rl and R2 other than hydrogen, or Rl and R2, Rla and R2a or R3 and R4 may together with the nitrogen atom to which they are attached form a piperidine, morpholine or pyrrolidine ring, and A~3 is an anion, preferably chloride, sulphate or phosphate.
Most preferably, P is a hcnopolymer of allylamine tthe ccmpound of formula I in which R, Rl and R2 are all hydrogen) or of diallylamine (the ccmpound of formula III in which both R's and R
are all hydrogen), or a copolymer of these two compounds.
The proportion of P to T in the mixture according to the invention is such that a synergistic effect exists, that is, that the measured effect of the mixture is superior to the additive effect of the separate ccmponents. Preferably the mixture contains from 30:70 to 70:30 parts by weight of the components (measured as dry active material, as salt in the case of T, as free base in the case of P), more preferably frcm 40:60 to 60:40, particularly 50:50. The mixture is prepared by simple mixing of the components, preferably in the form of their aqueous solutions.
- 4 - ~ ~ Case 150-5159 The mixture according to the invention is useful for aftertreatment of dyed, printed or optically brightened substrates comprising leather or textile fibres containing hydroxy-, amino- or thiol groups. Preferred textile fibre substrates are of cellulosic 5 fibres, particularly cotton, alone or mixed with other natural or synthetic fibres for exa~ple polyester, polyamide, polyacrylonitrile, polypropylene, wool and silk.
~ hen used for aftertreabment of a deep dyeing, for example corresponding to 1/1 standard depth on cotton, the amount of mixture is preferably from 1.5% - 6~ more preferably 2~ - 5% by weight based on the weight of active ingredients in the mixture and the dry weight of the substrate. For lighter shades, approximately 30-50~ of the above quantities may be used.
The mixture is applied to the dyed, printed or brightened sub~trate by an exhaust process or by alternative methods such as padding, spraying, dipping, etc., exhaust application being preferred.
Typical application conditions are, for example, entering the substrate into the aftertreatment bath at room temperature, heating to 50-70C over 20-30 min. and holding at this temperature for a further 20-30 minutes. Application is carried out under alkaline conditions, preferably at pH 9-13, more preferably pH 10-12, and the alkali to adjust the pH (e.g. sodium hydroxide) is preferably added once the optimum fixing temperature has been reached. Preferably aftertreatment is carried out in the presence of an electrolyte, for example sodium chloride, in a quantity of 5 - 20 g/l.
The aftertreated substrate is rinsed, neutralized and dried by conYentional means. The dyed substrate may be aftertreated directly from the dyebath, after a rinsing step or after an intermediate drying step.
The pol~meric ccmpounds P are known and are described for example in published European Patent Applications 95 233, 140 309, 142 337 and 145 220. A particularly preferred ccmpound P is a ~ 3 0 8 5 2 ~ Case 150-5159 water-soluble homo-polymer of mono-allylamine, prepared by polymerization of allylamine hydrochloride in the presence of an initiator containing an azo group and a group with a cationic nitrogen atcm. A further preferred polymer P is a water-soluble hcmopolymer of diallylamine, pre~ared by polymerization of diallylamine hydrochloride in the presence of the same type o~
initiator and also of a regulator as described in British Patent Application 2 192 893A. The resulting polymer has a viscosity of 500 mPa (Brookfield viscometer, spindle no. 4, 100 rpm) to 10,000 mPa 10 (srookfield, spindle no. 3, 10 rpm) in 55% - 65% wt. aqueous solution at room temperature.
The nature of the anionic or sulphur dye is not critical. The anionic dye may be of the type listed in Colour Index as C.I. Acid Dyes, C.I. Direct Dyes or C.I. Reactive Dyes : particularly useful 15 dyes are those given in British Patent 2 070 On6s. Suitable sulphur dyes are given in Colour Index and especially in US Patent 4 615 707.
The textile auxiliary T may be prepared by the addition of epichlorohydrin to aqueous ammonia at temperatures between 50C and 90C in a suitable vessel. After reaction excess ammonia is removed by distillation, and subsequently crosslinking is carried out by reaction with a further quantity of epichlorohydrin. When the initial mole ratio of the reactants is 4:9 ECH:NH3, it is found that approximately 1-1.5 moles of ammonia is recovered, so that the mole ratio actually reacted in step 1) is 4:7.5-8.
Many basic aftertreatment agents for improving the fastness properties of dyeings on cellulose fibres are known, but most do not exhibit sufficiently good wet fastness properties such as fastness to water, washing and perspiration. Practically all basic aftertreatment agents have the disadvantages that they have a negative effect upon the light fastness of the dyeing and may cause changes of shade.
Although the polymers P are reasonably effective fixing agents, textile auxiliary T has no such properties, being normally employed as a levelling agent in dyebaths. It is therefore surprising that a 6 - ~ ~C)&52~ Case 150-5159 combination of P and T has considerably better fixation properties (especially wet fastness properties of the treated dyeings) than P
alone, and that the ccmbination is largely free of the disadvantages of most other cationic fixing agents.
The following Examples in which all parts and percentages are by weight and all temperatures are in degrees Centigrade illustrate the invention.
' !.
~ hen used for aftertreabment of a deep dyeing, for example corresponding to 1/1 standard depth on cotton, the amount of mixture is preferably from 1.5% - 6~ more preferably 2~ - 5% by weight based on the weight of active ingredients in the mixture and the dry weight of the substrate. For lighter shades, approximately 30-50~ of the above quantities may be used.
The mixture is applied to the dyed, printed or brightened sub~trate by an exhaust process or by alternative methods such as padding, spraying, dipping, etc., exhaust application being preferred.
Typical application conditions are, for example, entering the substrate into the aftertreatment bath at room temperature, heating to 50-70C over 20-30 min. and holding at this temperature for a further 20-30 minutes. Application is carried out under alkaline conditions, preferably at pH 9-13, more preferably pH 10-12, and the alkali to adjust the pH (e.g. sodium hydroxide) is preferably added once the optimum fixing temperature has been reached. Preferably aftertreatment is carried out in the presence of an electrolyte, for example sodium chloride, in a quantity of 5 - 20 g/l.
The aftertreated substrate is rinsed, neutralized and dried by conYentional means. The dyed substrate may be aftertreated directly from the dyebath, after a rinsing step or after an intermediate drying step.
The pol~meric ccmpounds P are known and are described for example in published European Patent Applications 95 233, 140 309, 142 337 and 145 220. A particularly preferred ccmpound P is a ~ 3 0 8 5 2 ~ Case 150-5159 water-soluble homo-polymer of mono-allylamine, prepared by polymerization of allylamine hydrochloride in the presence of an initiator containing an azo group and a group with a cationic nitrogen atcm. A further preferred polymer P is a water-soluble hcmopolymer of diallylamine, pre~ared by polymerization of diallylamine hydrochloride in the presence of the same type o~
initiator and also of a regulator as described in British Patent Application 2 192 893A. The resulting polymer has a viscosity of 500 mPa (Brookfield viscometer, spindle no. 4, 100 rpm) to 10,000 mPa 10 (srookfield, spindle no. 3, 10 rpm) in 55% - 65% wt. aqueous solution at room temperature.
The nature of the anionic or sulphur dye is not critical. The anionic dye may be of the type listed in Colour Index as C.I. Acid Dyes, C.I. Direct Dyes or C.I. Reactive Dyes : particularly useful 15 dyes are those given in British Patent 2 070 On6s. Suitable sulphur dyes are given in Colour Index and especially in US Patent 4 615 707.
The textile auxiliary T may be prepared by the addition of epichlorohydrin to aqueous ammonia at temperatures between 50C and 90C in a suitable vessel. After reaction excess ammonia is removed by distillation, and subsequently crosslinking is carried out by reaction with a further quantity of epichlorohydrin. When the initial mole ratio of the reactants is 4:9 ECH:NH3, it is found that approximately 1-1.5 moles of ammonia is recovered, so that the mole ratio actually reacted in step 1) is 4:7.5-8.
Many basic aftertreatment agents for improving the fastness properties of dyeings on cellulose fibres are known, but most do not exhibit sufficiently good wet fastness properties such as fastness to water, washing and perspiration. Practically all basic aftertreatment agents have the disadvantages that they have a negative effect upon the light fastness of the dyeing and may cause changes of shade.
Although the polymers P are reasonably effective fixing agents, textile auxiliary T has no such properties, being normally employed as a levelling agent in dyebaths. It is therefore surprising that a 6 - ~ ~C)&52~ Case 150-5159 combination of P and T has considerably better fixation properties (especially wet fastness properties of the treated dyeings) than P
alone, and that the ccmbination is largely free of the disadvantages of most other cationic fixing agents.
The following Examples in which all parts and percentages are by weight and all temperatures are in degrees Centigrade illustrate the invention.
' !.
7 1 3 0 3 5 2 0 Case 150-5159 EXAMPLES
Example 1: Preparation of textile auxiliary T
370 Parts of 8.4 ~ aqueous a~monia solution are heated under nitrogen to 60 and 76 parts epichlorohydrin are gradually added over 2-3 hr, maintaining the t~mperature at 60-65. The mixture is then heated for 1 hr at 60-65 and finally 5 hr at 90.
The temperature is raised to 100 and 25-30 parts aqueous anmonia are distilled off, The mixture is cooled to 20, 8~ parts 30%
aqueous caustic soda are added and a further 90-100 parts of aqueous a~monia are removed by distillation at 60-70 under vacuum, until all ammonia is removed.
To the resulting product at 30 is added 50 parts water and 7.7 parts epichlorohydrin, and the mixture is heated to 90, stirred 1 hr at this tenperature, cooled, neutralised to pH 6.5-7.5 with 23 parts 65~ sulphuric acid, and adjusted to 30~ wt active material by adding water.
Example 2: Preparation of polymer P
a) To 193.9 parts of a solution of diallylamine hydrochloride in water (68.85 % concentration) is added 8.2 parts phosphorous acid and the mixtuee is heated to 65 undee niteogen. A
solution of 3.5 paets 2,2'-azo-bis-(2-amidinopeopane) dihydrochloride in 19.8 parts water is added dropwise over 19 hours. The mixture is stirred for a further 21 hours at 65, then heated to 95-100, stirred for 2 hours and cooled.
The resulting 59.2 ~ solution of polymer hydrochloride has a Brookfield viscosity of 1540 mPa (spindle No. 4, 50 rpm). By addition of 142 parts of 30 ~ aqueous sodium hydroxide with stirring, the free polyamine base is obtained (367 parts of a 26.4 % solution). The viscosity of this solution is 630 mPa (Brookfield, spindle No. 4, 100 rpm).
Example 1: Preparation of textile auxiliary T
370 Parts of 8.4 ~ aqueous a~monia solution are heated under nitrogen to 60 and 76 parts epichlorohydrin are gradually added over 2-3 hr, maintaining the t~mperature at 60-65. The mixture is then heated for 1 hr at 60-65 and finally 5 hr at 90.
The temperature is raised to 100 and 25-30 parts aqueous anmonia are distilled off, The mixture is cooled to 20, 8~ parts 30%
aqueous caustic soda are added and a further 90-100 parts of aqueous a~monia are removed by distillation at 60-70 under vacuum, until all ammonia is removed.
To the resulting product at 30 is added 50 parts water and 7.7 parts epichlorohydrin, and the mixture is heated to 90, stirred 1 hr at this tenperature, cooled, neutralised to pH 6.5-7.5 with 23 parts 65~ sulphuric acid, and adjusted to 30~ wt active material by adding water.
Example 2: Preparation of polymer P
a) To 193.9 parts of a solution of diallylamine hydrochloride in water (68.85 % concentration) is added 8.2 parts phosphorous acid and the mixtuee is heated to 65 undee niteogen. A
solution of 3.5 paets 2,2'-azo-bis-(2-amidinopeopane) dihydrochloride in 19.8 parts water is added dropwise over 19 hours. The mixture is stirred for a further 21 hours at 65, then heated to 95-100, stirred for 2 hours and cooled.
The resulting 59.2 ~ solution of polymer hydrochloride has a Brookfield viscosity of 1540 mPa (spindle No. 4, 50 rpm). By addition of 142 parts of 30 ~ aqueous sodium hydroxide with stirring, the free polyamine base is obtained (367 parts of a 26.4 % solution). The viscosity of this solution is 630 mPa (Brookfield, spindle No. 4, 100 rpm).
- 8 - I 3 ~ 8 5 2 0 case 150-5159 b) Example a) is repeated using 4.1 parts phosphorous acid instead of 8.2 parts. The resulting polymer dihydrochloride solution (6003 ~) has a srookfield viscosity of 2950 mPa ~spindle No. 4, 20 rpm). Dilution with 215 parts water and addition of 265.2 parts of 30 % sodium hydroxide solution gives a 21 ~ aqueous solution of the pol~mer base, having a Brookfield viscosity of 225 mPa (spindle No. 3, 100 rpm).
c) 498.7 Parts of 75 ~ aqueous allylamine hydrochloride solution and 793.5 parts of an 67.3 % aqueous solution of diallylamine hydrochloride are mixed under nitrogen and heated under nitrogen to 65. A solution of 31.5 parts 1,2'-azo-bis-(2-amidinopropane)dihydrochloride in 175.5 parts water is prepared, and 1/10 of this solution (21 parts) is added to the monomer solution while stirring vigorously. An exothermic polymerization reaction begins, and the reaction mixture is kept to 65-75 by cooling. After the exotherm subsides, but no sooner than 11/2 hrs, a further 21 parts of the initiator solution is added, and this procedure is continued After four additions of initiator there is practivally no further exotherm. After all the initiator has been added, the mixture is stirred for a further 3 hr at 75, then cooled. The resulting solution is neutralised with 106.S
parts 30 % sodium hydroxide solution and diluted with 181.3 parts water, giving 1790 parts of a viscous liquid containing 34.4 ~ of free polyamine.
d) 1000 Parts of a 70 % aqueous solution of monoallylamine hydrochloride are reacted with a solution of 17.5 parts 2,2'-azo-bis-(2-amidinopropane) in 37.5 parts of water as follows:
After heating the monomer solution to 50 under an inert atmosphere, half of the initiator solution (27.5 parts) is added.
c) 498.7 Parts of 75 ~ aqueous allylamine hydrochloride solution and 793.5 parts of an 67.3 % aqueous solution of diallylamine hydrochloride are mixed under nitrogen and heated under nitrogen to 65. A solution of 31.5 parts 1,2'-azo-bis-(2-amidinopropane)dihydrochloride in 175.5 parts water is prepared, and 1/10 of this solution (21 parts) is added to the monomer solution while stirring vigorously. An exothermic polymerization reaction begins, and the reaction mixture is kept to 65-75 by cooling. After the exotherm subsides, but no sooner than 11/2 hrs, a further 21 parts of the initiator solution is added, and this procedure is continued After four additions of initiator there is practivally no further exotherm. After all the initiator has been added, the mixture is stirred for a further 3 hr at 75, then cooled. The resulting solution is neutralised with 106.S
parts 30 % sodium hydroxide solution and diluted with 181.3 parts water, giving 1790 parts of a viscous liquid containing 34.4 ~ of free polyamine.
d) 1000 Parts of a 70 % aqueous solution of monoallylamine hydrochloride are reacted with a solution of 17.5 parts 2,2'-azo-bis-(2-amidinopropane) in 37.5 parts of water as follows:
After heating the monomer solution to 50 under an inert atmosphere, half of the initiator solution (27.5 parts) is added.
9 1 3 0 ~ 5 2 OCase 150-5159 After 30 hours polymerisation, the second half of the initiator solution is added. ~fter a further 30 hr the polyallylamine hydrochloride is obtained as a water-free white powder by precipitation in methanol.
5 e) 228 Parts of allylamine are cooled to S-10 and sl~wly reacted with 389 parts of 37 % aqueous hydrochloric acid, with external cooling. The salt solution is wanmed to 70O under nitrogen, and a solution of 14 parts of 2,2'-azo-bis-(2-amidino-propane) dihydrochloride in 80 parts water is added continuously over 20 hr. After addition is complete the mixture is stiered for a further 10 hr at 70, then 2 hr at 90, and finally cooled to giVe 711 parts of polyallylamide hydrochloride solution containing 52.6 % polyallylamine hydrochloride, corresponding to 32 % free Polyallylamine base.
Example 3 a) 50 Parts of the product of Example 2 e) are stirred at 300 with 50 parts of the product of Example 1, until a clear solution is obtained.
b) - e) 2D Examples 2 a) and b) are carried out with adjustment of the water content so that aqueous solutions containing 30-35 %
of polymer as free polyamine are obtained. The solid product of Example 2 d) is dissolved in water to give a solution containing 30-35 % of polymer as free polyamine. Example 3 a) is repeated, using in place of 50 parts of the product of Example 2 e), 50 parts of the product d Examples 2 a) - d), in the form of 30-35 % aqueous solution.
Application Example ~
A 100 ~ cotton knit fabric is dyed with 3 % of the dye of 30 Example 3 of US Patent 4 475 918, and aftertreated in an exhaust process at a goods-to-liquor ratio of 1:20 with 3 % of the product of 1 30~520 - 10- Case 150-5159 Example 3 a). The bath contains 10 g/l sodium chloride and 2 g/l sodium hydroxide, to give a pH value of 12. The bath is initially at rocm temperature and is raised to 60 over 20 minutes. Finally the goods are rinsed, neutralized with acetic acid, rinsed again, and dried in conventional manner.
A blue dyeing with excellent wet fastness properties is obtained, whereby the shade following the aftertreatment is practically identical with the shade before treatment.
Good results are also obtained when 2 % of the product of Example 3 a) is used.
Application Example B
Example A is repeated, using 4.5 % of the mixture of Example 3 a) on a 3 ~ dyeing with the reactive dyestuff of Example 5 of US Patent 4 475 918. A dyeing with excellent wet fastness and fastness to oxidizing agents is obtained.
By comparison the same dyeing without aftertreatment, or aftertreated with either polymer P or textile auxiliary T alone has significantly poorer wet fastness properties. Furthermore, such dyeings have inadequate fastness to perborate and chlorine.
Application Example C
A 1/1 standard depth dyeing of C.I. Leuco Sulfur Blue 13, aftertreated with 2 % of the product of Example 3 a) according to the process of Example A, has excellent wet fastness properties.
5 e) 228 Parts of allylamine are cooled to S-10 and sl~wly reacted with 389 parts of 37 % aqueous hydrochloric acid, with external cooling. The salt solution is wanmed to 70O under nitrogen, and a solution of 14 parts of 2,2'-azo-bis-(2-amidino-propane) dihydrochloride in 80 parts water is added continuously over 20 hr. After addition is complete the mixture is stiered for a further 10 hr at 70, then 2 hr at 90, and finally cooled to giVe 711 parts of polyallylamide hydrochloride solution containing 52.6 % polyallylamine hydrochloride, corresponding to 32 % free Polyallylamine base.
Example 3 a) 50 Parts of the product of Example 2 e) are stirred at 300 with 50 parts of the product of Example 1, until a clear solution is obtained.
b) - e) 2D Examples 2 a) and b) are carried out with adjustment of the water content so that aqueous solutions containing 30-35 %
of polymer as free polyamine are obtained. The solid product of Example 2 d) is dissolved in water to give a solution containing 30-35 % of polymer as free polyamine. Example 3 a) is repeated, using in place of 50 parts of the product of Example 2 e), 50 parts of the product d Examples 2 a) - d), in the form of 30-35 % aqueous solution.
Application Example ~
A 100 ~ cotton knit fabric is dyed with 3 % of the dye of 30 Example 3 of US Patent 4 475 918, and aftertreated in an exhaust process at a goods-to-liquor ratio of 1:20 with 3 % of the product of 1 30~520 - 10- Case 150-5159 Example 3 a). The bath contains 10 g/l sodium chloride and 2 g/l sodium hydroxide, to give a pH value of 12. The bath is initially at rocm temperature and is raised to 60 over 20 minutes. Finally the goods are rinsed, neutralized with acetic acid, rinsed again, and dried in conventional manner.
A blue dyeing with excellent wet fastness properties is obtained, whereby the shade following the aftertreatment is practically identical with the shade before treatment.
Good results are also obtained when 2 % of the product of Example 3 a) is used.
Application Example B
Example A is repeated, using 4.5 % of the mixture of Example 3 a) on a 3 ~ dyeing with the reactive dyestuff of Example 5 of US Patent 4 475 918. A dyeing with excellent wet fastness and fastness to oxidizing agents is obtained.
By comparison the same dyeing without aftertreatment, or aftertreated with either polymer P or textile auxiliary T alone has significantly poorer wet fastness properties. Furthermore, such dyeings have inadequate fastness to perborate and chlorine.
Application Example C
A 1/1 standard depth dyeing of C.I. Leuco Sulfur Blue 13, aftertreated with 2 % of the product of Example 3 a) according to the process of Example A, has excellent wet fastness properties.
Claims
PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A synergistic mixture containing as active ingredients a textile auxiliary (T) and a polymeric compound (P), in which T is the product of a 2-step reaction comprising the steps of 1) reacting an epihalohydrin with aqueous ammonia at 50-90°C in an initial mole ratio of 4 moles epihalohydrin to 8-10 moles of ammonia, and 2) reacting the product of step 1), after removal of excess ammonia, with a further 0.1 to 0.5 moles of epihalohydrin and P is a water-soluble homopolymer of a mono- or di-allylamine, or a water-soluble copolymer consisting of mono-, di- or tri-allylamine units.
2. A mixture according to Claim 1 in which T is the product of reacting epichlorohydrin with ammonia in an initial mole ratio of 4 moles epichlorohydrin to 9 moles ammonia, further reacted with 0.4 moles epichlorohydrin.
3. A mixture according to Claim 1 in which polymer P is a) a homopolymer of a monoallylamine or b) a homopolymer of a diallylamine or c) a copoplymer of monomer units selected from monoallylamines, diallylamines and triallylamines, in which any monoallylamine component is of formula I
I
or an acid addition salt thereof, or of formula II
II;
- 12 - 150-5159/Canada any diallylamine component is of formula III
or an acid addition salt thereof, or of formula IV
and any triallylamine component is of formula V
or an acid addition salt thereof, or of formula VI
in which R is hydrogen or methyl, preferably hydrogen R1 and R2 are independently hydrogen, C1-4alkyl, benzyl, 2-hydroxyethyl, 2-hydroxypropyl, 3-hydroxypropyl or cyclohexyl, R1a, R2a, R3 and R4, independently, have any significance of R1 and R2 other than hydrogen, - 13 - 150-5159/Canada or R1 and R2, R1a and R2a or R3 and R4 may together with the nitrogen atom to which they are attached form a piperidine, morpholine or pyrrolidine ring, and A? is an anion.
4. A mixture according to Claim 3 in which polymer P is a homopolymer of the compound of formula I or III in which R, R1 and R2 are all hydrogen, or a copolymer of these two compounds.
5. A mixture according to Claim 4 in which polymer P is a homopolymer of monoallylamine.
6. A mixture according to Claim 1 in which the weight ratio of P to T is from 30:70 to 70:30.
7. A process for aftertreatment of dyed, printed or optically brightened substrates comprising leather or textile fibres containing hydroxy-, amino- or thiol groups, comprising the step of treating the substrate with a mixture according to Claim 1.
8. A process according to Claim 7 in which the mixture is applied to the substrate from an exhaust bath at pH 9-13.
9. A process according to Claim 7 in which the substrate comprises cellulosic textile fibres dyed with an acid dye, a direct dye, a reactive dye or a sulphur dye.
10. An aqueous solution of a mixture of (T) and (P) wherein the mixture of (T) and (P) is defined as in
Claim 1.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DEP3706176.3 | 1987-02-26 | ||
DE19873706176 DE3706176A1 (en) | 1987-02-26 | 1987-02-26 | MIX WITH SYNERGISTIC PROPERTIES |
Publications (1)
Publication Number | Publication Date |
---|---|
CA1308520C true CA1308520C (en) | 1992-10-13 |
Family
ID=6321809
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CA000559875A Expired - Lifetime CA1308520C (en) | 1987-02-26 | 1988-02-25 | Textile aftertreatment agents |
Country Status (9)
Country | Link |
---|---|
US (1) | US4838896A (en) |
EP (1) | EP0280655B1 (en) |
JP (1) | JPH0633584B2 (en) |
AT (1) | ATE87675T1 (en) |
AU (1) | AU599457B2 (en) |
CA (1) | CA1308520C (en) |
DE (2) | DE3706176A1 (en) |
ES (1) | ES2041829T3 (en) |
ZA (1) | ZA881390B (en) |
Families Citing this family (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4855725A (en) | 1987-11-24 | 1989-08-08 | Fernandez Emilio A | Microprocessor based simulated book |
DE3938918A1 (en) * | 1989-11-24 | 1991-05-29 | Sandoz Ag | Synergistic mixt. for treating textiles before dyeing, foularding, etc - comprises poly epihalohydrin and poly:alkylene-poly:amine amine, derived from an allyl] amine, and textile auxiliary |
DE59103947D1 (en) * | 1990-03-15 | 1995-02-02 | Ciba Geigy Ag | Process for improving the yield and wet fastness of dyeings or prints produced with anionic dyes on cellulose fiber material. |
DE4105772A1 (en) * | 1991-02-23 | 1992-08-27 | Cassella Ag | METHOD FOR DYING LEATHER WITH WATER-INSOLUBLE SULFUR DYES |
GB9202375D0 (en) * | 1992-02-05 | 1992-03-18 | Ici Plc | Process |
DE59302811D1 (en) * | 1992-10-01 | 1996-07-11 | Ciba Geigy Ag | Process for dyeing wool-containing fiber materials |
DE19509982A1 (en) * | 1995-03-18 | 1996-09-19 | Sandoz Ag | Textile aftertreatment |
US6268452B1 (en) * | 1998-04-17 | 2001-07-31 | Nitto Boseki Co., Ltd. | Process for the production of allylamine polymer |
CN101302268B (en) * | 2008-07-03 | 2010-12-08 | 华东理工大学 | Non-formaldehyde organosilicon color fixing agent |
CN103709326B (en) * | 2013-12-27 | 2016-04-13 | 福建清源科技有限公司 | A kind of preparation method of cation type organic silicon modified Poly Dimethyl Diallyl Ammonium Chloride laking agent |
CN103922944B (en) * | 2014-04-01 | 2016-08-17 | 浙江传化股份有限公司 | A kind of crosslinkable quaternary ammonium salt water-soluble cationic monomer and its preparation method and application |
WO2018190328A1 (en) * | 2017-04-14 | 2018-10-18 | 日東紡績株式会社 | Wet rubbing fastness improver for cellulose-based fibers, method for producing dyed cellulose fiber using same, and use of same |
Family Cites Families (17)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CH448015A (en) * | 1965-11-09 | 1967-08-31 | Cassella Farbwerke Mainkur Ag | Process for improving the wet fastness properties of dyeings and prints produced with sulfur dyes on cellulose textile fibers |
US4054542A (en) * | 1975-04-14 | 1977-10-18 | Buckman Laboratories, Inc. | Amine-epichlorohydrin polymeric compositions |
CH631589B (en) * | 1976-12-07 | Sandoz Ag | PROCESS FOR INCREASING THE AFFINITY FOR ANIONIC COLORS AND OPTICAL BRIGHTENERS OF TEXTILE MATERIAL. | |
GB2084597B (en) * | 1980-09-24 | 1984-09-19 | Sandoz Ltd | Quaternary polyalkylene polyamine n-methylol resin reaction products and dye after-treatments |
CH673195B5 (en) * | 1981-05-14 | 1990-08-31 | Sandoz Ag | |
US4511707A (en) * | 1981-05-14 | 1985-04-16 | Sandoz Ltd. | Water-soluble precondensates useful for improving the fastness of dyes and optical brighteners on hydroxy group-containing substrates |
JPS5876585A (en) * | 1981-11-02 | 1983-05-09 | 三洋化成工業株式会社 | Agent and method of increasing wet fastness |
US4504640A (en) * | 1982-05-19 | 1985-03-12 | Nitto Boseki Co., Ltd. | Process for producing monoallylamine polymer |
JPS5966600A (en) * | 1982-06-30 | 1984-04-16 | ハ−キユリ−ズ・インコ−ポレ−テツド | Floor finishing felt composition and production thereof |
US4624743A (en) * | 1983-06-24 | 1986-11-25 | Weyerhaeuser Company | Cationic cellulose product and method for its preparation |
US4528347A (en) * | 1983-11-10 | 1985-07-09 | 501 Nitto Boseki, Co. Ltd | Process for producing polymers of monoallylamine |
JPS60110987A (en) * | 1983-11-15 | 1985-06-17 | 日東紡績株式会社 | Enhancement of dyeing fastness |
JPS60134080A (en) * | 1983-12-16 | 1985-07-17 | 一方社油脂工業株式会社 | Improvement in dyeability of fiber material, cationic fiber reactive product and its producton |
CA1220897A (en) * | 1984-01-11 | 1987-04-21 | Kiyoshi Shimizu | Process for producing polymers of monoallylamine |
US4624793A (en) * | 1984-06-20 | 1986-11-25 | National Distillers And Chemical Corporation | Fiber finishes |
JPS61231283A (en) * | 1985-04-01 | 1986-10-15 | 日東紡績株式会社 | Enhancement of dye fastness |
CH677857B5 (en) * | 1986-07-02 | 1992-01-15 | Sandoz Ag |
-
1987
- 1987-02-26 DE DE19873706176 patent/DE3706176A1/en not_active Withdrawn
-
1988
- 1988-02-01 US US07/151,032 patent/US4838896A/en not_active Expired - Fee Related
- 1988-02-24 DE DE8888810111T patent/DE3879734T2/en not_active Expired - Fee Related
- 1988-02-24 EP EP88810111A patent/EP0280655B1/en not_active Expired - Lifetime
- 1988-02-24 AT AT88810111T patent/ATE87675T1/en active
- 1988-02-24 JP JP63039737A patent/JPH0633584B2/en not_active Expired - Lifetime
- 1988-02-24 AU AU12139/88A patent/AU599457B2/en not_active Ceased
- 1988-02-24 ES ES198888810111T patent/ES2041829T3/en not_active Expired - Lifetime
- 1988-02-25 CA CA000559875A patent/CA1308520C/en not_active Expired - Lifetime
- 1988-02-26 ZA ZA881390A patent/ZA881390B/en unknown
Also Published As
Publication number | Publication date |
---|---|
ZA881390B (en) | 1989-10-25 |
DE3879734D1 (en) | 1993-05-06 |
AU1213988A (en) | 1988-09-01 |
DE3706176A1 (en) | 1988-09-08 |
EP0280655A3 (en) | 1989-11-23 |
JPS63227870A (en) | 1988-09-22 |
ATE87675T1 (en) | 1993-04-15 |
DE3879734T2 (en) | 1993-09-09 |
JPH0633584B2 (en) | 1994-05-02 |
AU599457B2 (en) | 1990-07-19 |
EP0280655A2 (en) | 1988-08-31 |
ES2041829T3 (en) | 1993-12-01 |
EP0280655B1 (en) | 1993-03-31 |
US4838896A (en) | 1989-06-13 |
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